AU2002228063B2

AU2002228063B2 - A ternary mixture of biodegradable polyesters and products obtained therefrom

Info

Publication number: AU2002228063B2
Application number: AU2002228063A
Authority: AU
Inventors: Catia Bastioli; Gianfranco Del Tredici; Italo Guanella; Tiziana Milizia; Roberto Ponti
Original assignee: Novamont SpA
Current assignee: Novamont SpA
Priority date: 2001-01-25
Filing date: 2002-01-25
Publication date: 2006-08-03
Anticipated expiration: 2022-01-25
Also published as: DE60200881D1; JP2004517204A; TWI265950B; KR100841577B1; CA2434849C; EP1355985A1; JP4842501B2; EP1355985B1; ATE272681T1; ES2225767T3; CA2434849A1; WO2002059198A1; US20040092672A1; CN1531573A; CN1277882C; US20120245259A1; NO20033333D0; DE60200881T2; KR20030078071A; NO20033333L

Abstract

The invention relates to a mixture of biodegradable polyesters comprising: (A) a polyhydroxy acid of the poly-ε-caprolactone type and its copolymers, (B) aliphatic polyester, and (C) a polymer of polylactic acid, in which the concentration of (A) varies with respect to (A+B) in the range between 40 and 70% by weight, and the concentration of (C) with respects to (A+B+C) lies between 2 and 30%.

Description

WO 02/059198 PCT/EP02/00737 A ternary mixture of biodegradable polyesters and products obtained therefrom The present invention relates to mixtures of biodegradable polyesters comprising at least three polyesters in proportions such that it is possible to obtain biodegradable films with improved characteristics with respect to the individual starting polyesters and, in particular, with significant properties of UV resistance, biaxial strength, that is longitudinally of and transverse the film-forming direction, and transparency, as well as biodegradability.

Films obtained from such mixtures are particularly useful as mulching films, in particular in the case of transparent films, or as layers for multi-layer film for improving the properties of UV resistance of the multi-layer film. Films can also be useful in food packaging or in bags for silage and for various applications.

Prior Art Conventional polymers such as low and high density polyethylene are characterised not only by an excellent flexibility and water resistance, but also by good transparency and optimum resistance to tearing. These polymers are used, for example, for sacks and bags, as packaging material and in the form of film for agricultural mulching. However, their low biodegradability has created a visual pollution problem which has been increasing in recent decades.

In the field of transparent film for mulching the need to combine a high strength, a rapid biodegradability and a UV CONFIRMATION COPY WO 02/059198 PCT/EP02/00737 2 resistance which allows the film to remain on the ground for at least one hundred and twenty days has made it difficult to identify biodegradable materials suitable for this purpose.

Polymers such as L-polylactic acid, D, L-polylactic acid, Dpolylactic acid and their copolymers are biodegradable thermoplastic materials, obtained from a renewable source, which are transparent and have excellent resistance to fungi and are therefore suitable for packaging food as well as for the preservation of its organoleptic characteristics. The said materials, however, biodegrade slowly in the ground and even in compost degrade quickly only at high temperatures.

The major limitation, however, is in the lack of tear resistance of thin films obtained in normal blown or cast head film-forming conditions. Moreover, their high rigidity makes them unsuitable as films for mulching, bags for food, refuse sacks and other films for packaging, which require high characteristics of strength. Their UV resistance on the other hand is excellent.

If polyesters constituted predominantly of monomers from renewable sources starting from diacids and diols, for example polymers of sebacic, brassylic and azelaic acid are considered, these have the enormous limitation of a strong anistropy in terms of tear resistance between the longitudinal and transverse directions and, moreover, are characterised by a very low longitudinal tear resistance.

For this reason films prepared from these resins are also inadequate for use as mulching, as refuse sacks etc. Their UV resistance is good, even if lower than the UV resistance of polylactic acid, whilst the rapidity of biodegrading is comparable with that of polylactic acid.

Polyhydroxyacids such as poly-e-caprolactone and its copolymers or long chain polyhydroxyalkanoates C 4 -C20, when in film form, also tend to become orientated in the longitudinal direction exhibiting further limits of filmability. As further limitations they tend to biodegrade ND quickly, especially in the ground. The UV stability is 00 similar to that of the above-described polymers from diacid- CI diol.

CI Binary mixtures of polylactic acid and aliphatic polyesters have been the subject of many patents. In particular, EP-0 980 894 Al (Mitsui Chemical) describes a significant improvement in tear resistance and balancing of the mechanical properties in film produced by the mixture of polylactic acid and polybutylen succinate in the presence of a plasticiser.

Those described, however, are non-transparent films, with a very modest strength, of the order of 120g in accordance with the JIS P8116 method. The presence of a plasticiser, moreover, places limitations on the use of the film in contact with food and, because of the ageing phenomena, on use in the agricultural mulching sector.

US Patent 5, 883 199 describes binary mixtures of polylactic acid and polyester, with a polylactic acid content between and 90% and the polyester in a continuous or co-continuous phase. Such mixtures, according to the described examples, have very low values of tear resistance.

4 It is to be clearly understood that although prior art publications are referred to herein, this reference does not constitute an admission that any of Sthese documents forms part of the common general knowledge in the art in Australia or in any other country.

Starting from the problem of finding a 0 biodegradable material able to combine properties of C transparency, tear resistance, UV resistance and complete C biodegradability, but with a rapidity of biodegrading compatible with applications such as transparent mulching, it has now been surprisingly found that by combining the three different types of polyesters described (polymer of lactic acid, polyester derived from diacids/diols and polyhydroxy acids such as poly-e-caprolactone or long chain C 4

-C

20 polyhydroxyalkanoates) in specific ratios there is a critical range of compositions in which it is possible to obtain a tear strength in the two directions comparable with conventional plastics materials such as polyethylene, a modulus of elasticity with values lying between those of low and high density polyethylene, and a high UV stability greater than that of polyesters from diacids/diols and or poly-e-caprolactone, and entirely similar to that of polylactic acid and its copolymers even for very low concentrations of polylactic acid. It is moreover found that the ternary mixture of polyesters according to the invention is able to maintain a transparency comparable with that of the individual starting materials even after stretching.

Summary of the Invention In a first aspect, the present invention provides a biodegradable mixture of polyesters comprising: a polyhydroxy acid or C 4

-C

20 long chain polyhydroxyalkanoates, a polyester of the diacid diol type with a molecular weight M, greater than 40,000 and a melting point of 40-125 0

C,

H:\IsabelH\Speci\50175.doc 10/07/06 5 0 a polymer of polylactic acid which contains at least 55% L-lactic or D-lactic acid or their combinations with a molecular weight Mw greater than 30,000 wherein the concentration of varies with respect to in the range of between 40 and 70% by weight, the concentration of with respect to (A+B+C) Slies between 2 and 30% by weight, and the mixture has a UV 00 stability measured on film of 25-30 pm and has an average Ce reduction in its tensile properties after 216 hours of exposure to UV rays less than 30% considered as the Saverage reduction in breaking load, elongation at breakage and longitudinal breaking energy.

The polyhydroxy acid may be a poly-ecaprolactone or copolymer thereof.

The polyester preferably has a molecular weight Mw greater than 60,000 and a melting point of 0 C, more preferably 55-90 0

C.

Preferably, the concentration of with respect to is 5-25% by weight.

Preferably, the polyhydroxy acid is biodegradable according to the CEN 13432 regulation, has (at T=23 0 C and a Relative Humidity of 55%) a modulus lying between 100 MPa and 1200 MPa, longitudinal breaking elongation greater than 20, more preferably greater than 100% and more preferably greater than 200%, for film produced by blown film formation having a thickness of and tested within 3 days from filming.

Preferably, the diacid/diol aliphatic polyester has (at T 23 0 C and Relative Humidity of 55%) a modulus of elasticity lying between 200 and 900 MPa and breaking elongation greater than 200%, more preferably greater than 300% for film with a thickness of 25-30pm produced by blown film formation and tested within 3 days from production.

Preferably, the polymer of the polylactic acid has a modulus of elasticity greater than 400 Mpa, more preferably greater than 800 Mpa.

H:\IsabelH\Speci\5015 .doc 10/07/06 6 Q) The mixture of biodegradable polyesters according to the present invention can be obtained by a process which involves working in a twin screw or single screw O extruder in temperature conditions lying between 140 and 200 0 C, with a single step procedure or even with a separate Smixing and subsequent film-forming process.

IDIn a second aspect, the present invention 00 provides a film produced from a mixture according to the C- first aspect of the present invention.

In the case of a film-forming process separate from the mixing process, the said operation can be achieved with the use, for film-forming, of conventional machines for extrusion of polyethylene (low of high density) with a temperature profile in the range between 140 and 200 0 C and more preferably between 185 and 195 0 C, a blowing ratio normally in the range 1.5-5 and a stretching ratio lying between 3 and 100, more preferably 3 and and allows film to be obtained with a thickness between and Preferably, films according to the second aspect of the present invention with a thickness lying between 25-30m have a bidirectional tear resistance according to the Elmendorf test of between 5 and 100 N/mm, more preferably between 7 and 90 N/mm and, still more preferably between 10 and 80 N/mm, preferably with a ratio of transverse to longitudinal Elmendorf values of between and 0.4, and more preferably between 3 and Preferably, such films have a modulus of elasticity lying between 200 and 1200 MPa, more preferably between 300 and 1000 MPa, and are biodegradable in the ground and in compost. Preferably, such films have characteristics of transparency expressed as transmittance at the entrance port measured on the HAZEGUARD SYSTEM XL-211 in the range between 85 and 95% when filmed at a head temperature lying between 185 and 200 0

C.

Moreover, the average reduction in the tensile properties after 216 hours of exposure of the film of H:\IabelH\Speci\SO175.doc 10/07/06 7 O 30m to a Philips ultraviolet lamp TL20W/12 is preferably less than 30% considered as the average of the reduction in the breakage load, the reduction in the breakage elongation and the reduction in the longitudinal breakage energy (measured according to ASTM D 882-91).

In the mixture phase polymers of type are I preferred with MFI (standard ASTM D 1238-89) lying between 00 1 and 10 dg/min, polymers of type are preferred with C- MFI lying between 1 and 10 dg/min and polymers of type (C) are preferred with MFI lying between 2 and 30 dg/min.

The family of polymers of type includes polyesters obtained from hydroxy acids such as ecaprolactones and mixtures thereof with other monomers, such as hydroxy acids or diacids/diols, or even with prepolymers to obtain block polymers. They also include polycaprolactones with star structure or branched in any way, chain extended or partially cross linked. Included are also long chain C 4

-C

20 polyhydroxyalkanoates, such as polyhydroxybutirrates copolymerized with Cs-C 20 polyhydroxiacids comonomers, having tensile properties MPa, E comprised between 100 and 1200 Mpa and melting point between 50-160°C, preferably 60-145°C, more preferably between 62-125 0

C.

The polymer is constituted by dicarboxylic acids and diols and possibly by hydroxy acids. Examples of diacids are oxyalic, malonic, succinic, gluteric, adipic, pimelic, suberic, azelaic, sebacic, brassylic, undecandioic and dodecandioic acids. Azelaic acid, sebacic acid and brassylic acid and their mixtures are particularly preferred.

H:\SabelH\Speci\50175.doc 10/07/06 WO 02/059198 PCT/EP02/00737 8 Specific glycols are ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1, 2- and 1,3propylene glycol, dipropylene glycol, 1,3- butandiol, 1,4butandiol, 3- methyl-1, 5-pentandiol, 1, 6- hexandiol, 1, 9nonandiol, 1, 11-undecandiol, 1, 13- tridecandiol, neopentylglycol, polytetramethylene glycol, 1, 4- cyclohexan dimethanol and cyclohexandiol. These compounds can be utilised alone or in mixture.

Typical hydroxy acids include glycolic acid, lactic acid, 3hydroxy butyric, 4-hydroxy butyric, 3-hydroxy valeric, 4hydroxy valeric and 6-hydroxy caproic acid, and further include cyclic esters of hydroxycarboxylic acid such as glycolides, dimers of glycolic acid, e-caprolactone and 6hydroxycaproic acid. These compounds can be used alone or in mixtures. All the compounds described above are combined in such a way as to form polyesters with the mechanical characteristics of tensile resistance to elongation greater than 200% and preferably greater than 300% and modulus of elasticity lying between 200 and 900 MPa on blown films of at least 25-30 pm thickness and with a melting point between and 125 OC, preferably between 50 and 95 OC and more preferably between 55 and 90 OC. Particularly preferred are polyesters containing more than 50% moles, preferably more than 70% moles with respect to the total acid content, of azelaic acid, sebacic acid and brassylic acid and their mixtures.

The polymers of type also include polyamide polyesters where the polyester part is as described above and the polyamide part can be caprolactame, aliphatic diamine such as hexamethylene diamine or even an amino acid. The polyesters of type can also contain aromatic diacids in quantities WO 02/059198 PCT/EP02/00737 9 less than 5 mole%. Polymers of type also include polycarbonates.

Biodegradable polyesters forming part of the mixture according to the invention can be polymerised by polycondensation or, as in the case of glycolides and lactones, by ring opening, as is known in the literature.

Moreover, the polyesters can be polymers branched with the introduction of polyfunctional monomers such as glycerine, epoxydized soya oil, trimethylolol propane and the like or polycarboxylic acids such as butantetracarboxylic acid.

Moreover, the polyesters of type or may also have additives such as chain extenders, difunctional, trifunctional or tetrafunctional anhydrides such as maleic anhydride, trimellitic or pyromellitic anhydrides, with epoxy, isocyanate, aliphatic and aromatic groups.

Regrading with isocyanates can take place in the molten state for the purpose of the polymerisation reaction or in the extrusion phase, or in the solid state as described in the Novamont patent WO 99/28367. The three types of polymers and can also have additives such as chain extenders or cross linking agents of the type described above added to them in the mixing phase.

The material obtained from the mixing of the three polymers and has no need of plastisicers which create problems of migration especially for food packaging.

However, quantities of plasticisers less than 10% with respect to the polymers (B preferably less than 5% with respect to the total composition, can be added.

WO 02/059198 PCT/EP02/00737 Various additives such as antioxidants, UV stabilisers such as Lowilite Great Lake or Tinuvin Ciba, heat stabilisers and hydrolysis stabilisers, flame retardants, slow release agents, organic and inorganic fillers such as, for example, natural fibres, anti-static agents, humectants, colorants and lubricants can also be incorporated in the mixture.

In particular, in the production of blown or cast film it is possible to add silica, calcium carbonate, talc, kaolin, kaolinite, zinc oxide, various wollastonites and in general lamellar inorganic substances, whether or not functionalised with organic molecules, capable of delamellating in the mixing phase with the polymer mixture or with one of the individual polymers of the mixture to give nanocomposites with improved anti blocking and barrier properties. The various inorganic substances can be used in mixtures or with individual products. The concentration of the inorganic additives is generally between 0.05 and 70%, preferably between 0.5 and 50%, more preferably between 1 and In the case of fibres and natural fillers such as cellulose fibres, sisal, ground nuts, maize husks, rice, or soya chaff and the like the preferred concentrations lie in the range to 70%, more preferably from 1-50%. It is also possible to fill these materials with mixed inorganic and vegetable fillers.

The compositions according to the present invention can be advantageously mixed with destructurised or complexed starch or with proteins or lignin.

To improve the film-forming characteristics amides of aliphatic acids such as oleamide, stearamide, erucamide, WO 02/059198 PCT/EP02/00737 11 behenamide, N-oleylpalmitamide, N-stearylerucamide and other amides, salts of fatty acids such as stearates of aluminium, zinc or calcium and the like can be added. The quantities of these additives vary from 0.05 to 7 parts and preferably between 0.1 and 5 parts of the mixture of polymers.

The mixture thus obtained can be transformed into a film by blowing or extrusion with a flat head. The transparent film is strong and perfectly weldable. It can be obtained in thicknesses to 5 pm by blowing or casting. The film can be transformed into sacks, carrier bags, film and bags for packaging food, extensible film and heat-shrink film, film for adhesive tapes, for nappies, for coloured ornamental tapes. Other principle applications are sacks for silage, sacks for fruit and vegetables with good breathbility, sacks for bread and other foods, films for covering trays of meat, cheese and other foods, and pots for yoghurt. The film can also be biorientated.

The film obtained from the compositions according to the present invention can moreover be utilised as components of multi layer films composed of at least one layer of polylactic acid or from other polyesters, de-structured or non-de-structured starch and its blends with synthetic and natural polymers, or as a component of a multi layer with aluminium and other materials or with a vacuum-metalised layer with aluminium, silica and other inorganic materials.

The multi layers can be obtained by co-extrusion, lamination or extrusion coating, if one layer is paper, woven or nonwoven textile, another layer of biodegradable material or other material which does not melt at the extrusion temperature of the film. The layer constituted by the material of the present invention will have the WO 02/059198 PCT/EP02/00737 12 characteristic of a high resistance to UV even without the introduction of any UV stabiliser. This is a particularly important factor for a biodegradable film which must degrade in the ground without leaving residues.

The mixture of the present invention can be used in the form of at least one layer of a multi layer film in which at least one other layer can comprise an aliphatic-aromatic polyester, in particular polyalkylene terephthalate-adipate or polyalkylene terephthalate-adipate-succinate and the like, preferably with a teraphthalic acid content with respect to the sum of acids less than 60 mole or a blend thereof with de-structured starch or with polylactic acid or their combinations. The layer other than the mixture according to the invention can also be constituted by destructured starch suitably plasticised and/or complexed.

The films can be used for agricultural mulching, green-house cladding, packaging for straw and various forages. They can also contain UV stabilisers, they can be in the form of individual films or co-extruded, as in the case of materials based on starch, to give improved UV resistance, improved barrier properties, and slower degradation under atmospheric agents and in the soil. The material obtained can also be utilised to obtain fibres for woven and non-woven textiles or for fishing nets. Moreover, the non-woven fabric can be used in the sector of nappies, sanitary towels etc. The fibres can also be utilised as weldable reinforcing fibres in special papers. The material can be utilised with success also for the production of extruded or co-extruded sheets for thermoforming with other layers of polymers such as polylactic acid, other polyesters or polyamides, materials WO 02/059198 PCT/EP02/00737 13 based on starch and other materials and then thermoformed into trays for food, agricultural containers and others.

The material can have additives such as polymeric additives like waxes, polyethylene and polypropylene, PET and PBT, polystyrene, copolymers of ethylene and propylene with functional carboxylic, carboxylate, methacrylate, acrylate groups, or hydroxylic groups, or combined with these polymers in coextrusion, coinjection or the like. The material can be utilised as a matrix in a blend with de-structured starch according to the processes described in EP-0 327 505, EP-539 541, EP-0 400 532, EP-0 413 798, EP-0 965 615 with the possibility of forming complexes with starch.

They can be utilised as coating films for biodegradable foam materials based on polyesters, polyamides, thermoplastic starches, complex starches or simply blends of starch with other polymers or with the material of the present invention.

The material, on its own or in mixture with starch or other polymers, can be obtained as a foam material to produce containers for fruit and vegetables, meat, cheese and other food products, containers for fast food or in the form of expanded agglomerable beads for expanded moulded work pieces for industrial packaging. They can be used as foam materials in place of expanded polyethylene. They can also find applications in the non-woven and woven textile fibre sector for clothing, sanitary products and industrial applications, as well as in the sector of fishing nets or nets for fruit and vegetables. The compositions according to the present invention can be advantageously used also in the injection molding field for example in ordr to produce cutlery, food containers, and so on.

WO 02/059198 PCT/EP02/00737 14 The mixture of biodegradable polyesters according to the invention will now be illustrated by means of several nonlimitative examples.

Examples Example 1 Polymers constituting the mixture: 50% poly-e-caprolactone Union Carbide Tone 787; 40% aliphatic polyester polybutylene sebacate produced from sebacic acid and butandiol with monobutylstannoic acid catalyst according to example 1 of WO 00/55236: 10% polymer of polylactic acid 4040 Cargill with a 6% content of D-lactic (MFI 4 dg/min).

Mixing of polymers in OMC extruder: 58 mm diameter; L/D 36; rpm 160; temperature profile 120-160 x 5 155 x 2 Consumption 80A, flow rate 40 Kg/h Filmformation on a Ghioldi machine; Diameter 40 mm, L/D 30, rpm 45; die: diameter 100mm; air gap 0.9mm; land 12; flow rate 13.5 Kg/h; temperature profile: 110-130-145 x 2; temperature filter 190 x 2; head temperature 190 x 2.

Film: width 400 mm; thickness 25 pm.

Determination of the values of transmittance effected at the entrance port (Tentr) was made by means of the HAZEGUARD SYSTEM XL 211 measuring instrument.

The values of the modulus of elasticity breaking load breaking elongation and breaking energy (Enbreak) were determined in accordance with ASTM D 882 91 by means of an INSTRON 4502 instrument.

WO 02/059198 PCT/EP02/00737 The tensile properties were repeated at different exposure times to a Philips TL20W/12 UV lamp. In particular, samples in accordance with ASTM D 882-91 were fixed to a disc rotating at a speed of 40 revolutions per minute positioned at a distance of 12 cm from the UV lamp.

The results of the test were plotted in table 1. Examples 3a c and 4a b are comparison examples.

In example 5 polymer is polyhydroxybutyrate-valerate (Biopol) a copolymer of hydroxybutyric acid with 16% of hydroxyvaleric acid.

TABLE 1 Sample A B C A/ C/ Tentr UV exposure E 7 E Enbreak Average A+B A+B+C (hours) (MPa) (MPa) KJ/m 2 Reduction 1 50 40 10 55.5 10 92.9 0 652 32 638 7398 2 50 40 10 55.5 10 92.9 264 725 29 658 7347 2.3 3a 100 0 0 100 0 94.5 0 510 52 650 8500 3b 100 0 0 100 0 94.5 120 495 40 585 6350 19.5 3c 100 0 0 100 0 94.5 216 560 26 325 3200 54.1 4a 0 100 0 0 0 94 0 624 46 646 10330 4b 0 100 0 0 0 94 216 698 31.5 487 5961 32.8 40 50 10 44.4 10 0 980 31 120 820 40 50 10 44.4 10 216 1020 29 112 742 9.8

Claims

1. A biodegradable mixture of polyesters _O comprising: a polyhydroxy acid or C 4 -C 20 long chain M polyhydroxyalkanoates, IND a polyester of the diacid diol type with a 00 molecular weight Mw greater than 40,000 and a melting point Cq of 40-125 0 C, a polymer of polylactic acid which contains Sat least 55% L-lactic or D-lactic acid or their combinations with a molecular weight Mw greater than 30,000 wherein the concentration of varies with respect to in the range of between 40 and 70% by weight, the concentration of with respect to (A+B+C) lies between 2 and 30% by weight, and the mixture has a UV stability measured on film of 25-30 pm and has an average reduction in its tensile properties after 216 hours of exposure to UV rays less than 30% considered as the average reduction in breaking load, elongation at breakage and longitudinal breaking energy.

2. A mixture as claimed in claim 1 wherein the concentration of with respect to is 5-25% by weight.

3. A mixture as claimed in claim 1 or claim 2 wherein the aliphatic polyester has a modulus of elasticity of 200-900 MPa and a breaking elongation greater than 200% for film with a thickness of 25-30 pm produced by blown file formation.

4. A mixture as claimed in claim 3 wherein the aliphatic polyester has a breaking elongation greater than 300% for film with a thickness of 25-30 pm produced by blown file formation. H:\Iabe1H\Speci\50175.doc 6/07/06 18

5. A mixture as claimed in any one of the preceding clams wherein the polymer of polylactic acid (C) has a modulus of elasticity greater than 400 MPa.

6. A mixture as claimed in claim 5 wherein the Spolymer of polylactic acid has a modulus of elasticity I greater than 800 MPa. 00 C1 7. A mixture as claimed in any one of the preceding claims wherein the aliphatic polyester has a Smelting point of 50-95 0 C.

8. A mixture as claimed in claim 7 wherein the aliphatic polyester has a melting point of 55-90 0 C.

9. A mixture as claimed in any one of the preceding claims wherein the diacid content of the aliphatic polyester is azelaic acid, sebacic acid, brassylic acid, or mixtures thereof in concentrations, with respect to the total acid, greater than 50 mole%. A mixture as claimed in any one of claims 1-8 wherein the diacid content of the aliphatic polyester is azelaic acid, sebacic acid, brassylic acid, or mixtures thereof in concentrations, with respect to the total acid, greater than 70 mole%.

11. A mixture as claimed in any one of the preceding claims wherein the polyhydroxy acid is a poly-C-caprolactone or copolymer thereof.

12. A mixture as claimed in any one of the preceding claims, combined with de-structured starch, raw starch or modified starch wherein the starch is in dispersed phase, complexed or not complexed. H.\I8&abeH\Speci\SO17S.doc 6/07/06 19

13. substantially

14. in any one of bidirectional 5-100 N/mm.

16. bidirectional

17. bidirectional A mixture as claimed in claim 1 being as herein described. A film produced from a mixture as claimed the preceding claims. A film as claimed in claim 14 having a tear resistance with the Elmendorf test of A film as claimed in claim 15 having a tear resistance of 7-90 N/mm. A film as claimed in claim 15 having a tear resistance of 10-80 N/mm.

18. A film as claimed in any one of claims 17 wherein the ratio between the tear resistance values according to the Elmendorf test in the transverse and longitudinal directions lies between 4.5 and 0.4.

19. A film as claimed in any one of claims 14- 18 having a modulus of elasticity of 200-1200 MPa.

20. A film as claimed in claim 19 having a modulus of elasticity of 300-1000 MPa.

21. A multi layer film constituted by one or more layers of a film as claimed in any one of claims 14- 20 and at least one layer of material comprising aliphatic/aromatic polyester as such or in a blend with other polyesters and/or with de-structured starch.

22. A multi layer film as claimed in claim 21 wherein the aliphatic/aromatic polyester is polybutylene terephthalateadipate with a ratio between teraphthalic and adipic acid less than 65 mole%, in a blend with de- H:\IsabelH\Speci\50175.doc 6/07/06 20 0 structured starch and, optionally, polylactic acid.

23. Use of film as claimed in any one of claims 14-22 as a transparent agricultural mulch, as a green- house cover or for packaging straw and forage. NO 24. Use of film as claimed in any one of claims 00 14-22 for packaging food or for containing organic Cq residues. O 25. A solid sheet produced from a mixture as claimed in any one of claims 1-13.

26. An expanded sheet produced from a mixture as claimed in any one of claims 1-13.

27. Fibres produced from a mixture as claimed in any one of claims 1-13 for woven or non-woven textiles for use in industrial, clothing and sanitary sectors.

28. A coating material produced from a mixture as claimed in any one of claims 1-13. Dated this 10th day of July 2006 NOVAMONT S.P.A. By its Patent Attorneys GRIFFITH HACK H:\IsabelH\Speci\50175.doc 6/07/06